US10800862B2 - Amino silane-based compound, method of preparing the same, and modified conjugated diene-based polymer including the compound - Google Patents

Amino silane-based compound, method of preparing the same, and modified conjugated diene-based polymer including the compound Download PDF

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US10800862B2
US10800862B2 US16/307,213 US201716307213A US10800862B2 US 10800862 B2 US10800862 B2 US 10800862B2 US 201716307213 A US201716307213 A US 201716307213A US 10800862 B2 US10800862 B2 US 10800862B2
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amine
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Won Taeck Lim
Won Mun Choi
Seung Ho Choi
Ji Eun Kim
Dae June Joe
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LG Chem Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C08K5/544—Silicon-containing compounds containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/0803—Compounds with Si-C or Si-Si linkages
    • C07F7/081—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te
    • C—CHEMISTRY; METALLURGY
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    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
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    • C07F7/0834—Compounds having one or more O-Si linkage
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    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/0834—Compounds having one or more O-Si linkage
    • C07F7/0838—Compounds with one or more Si-O-Si sequences
    • C07F7/0872—Preparation and treatment thereof
    • C07F7/0876—Reactions involving the formation of bonds to a Si atom of a Si-O-Si sequence other than a bond of the Si-O-Si linkage
    • C07F7/0878—Si-C bond
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    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
    • C07F7/1804—Compounds having Si-O-C linkages
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    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
    • C07F7/1804—Compounds having Si-O-C linkages
    • C07F7/1872—Preparation; Treatments not provided for in C07F7/20
    • C07F7/1892—Preparation; Treatments not provided for in C07F7/20 by reactions not provided for in C07F7/1876 - C07F7/1888
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
    • C08C19/00—Chemical modification of rubber
    • C08C19/22—Incorporating nitrogen atoms into the molecule
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
    • C08C19/00—Chemical modification of rubber
    • C08C19/25—Incorporating silicon atoms into the molecule
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
    • C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
    • C08F236/10—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated with vinyl-aromatic monomers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/42—Introducing metal atoms or metal-containing groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C08K5/541—Silicon-containing compounds containing oxygen
    • C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
    • C08K5/5419—Silicon-containing compounds containing oxygen containing at least one Si—O bond containing at least one Si—C bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2810/00—Chemical modification of a polymer
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00—Road transport of goods or passengers
    • Y02T10/80—Technologies aiming to reduce greenhouse gasses emissions common to all road transportation technologies
    • Y02T10/86—Optimisation of rolling resistance, e.g. weight reduction 
    • Y02T10/862—

Definitions

  • the present invention relates to an amino silane-based compound, and more particularly, to an amino silane-based compound having an excellent interaction with a rubber polymer and an inorganic filler, a method of preparing the same, and a modified conjugated diene-based polymer in which excellent tensile strength, abrasion resistance, low fuel consumption property, and wet road surface resistance as well as high heat generation property are obtained by including a functional group derived from the amino silane-based compound.
  • a natural rubber, a polyisoprene rubber, or a polybutadiene rubber is known as a rubber material having a low hysteresis loss, but these rubbers may have low wet road surface resistance.
  • a conjugated diene-based polymer or copolymer such as a styrene-butadiene rubber (hereinafter, referred to as “SBR”) or a butadiene rubber (hereinafter, referred to as “BR”), is prepared by emulsion polymerization or solution polymerization to be used as a rubber for a tire.
  • the greatest advantage of the solution polymerization in comparison to the emulsion polymerization is that a vinyl structure content and a styrene content, which specify physical properties of the rubber, may be arbitrarily adjusted and its molecular weight and physical properties may be controlled by coupling or modification.
  • the SBR prepared by the solution polymerization is widely used as a rubber material for a tire because it is easy to change a structure of the finally prepared SBR or BR, and movement of chain ends may be reduced and a coupling force with a filler, such as silica or carbon black, may be increased by coupling or modification of the chain ends.
  • the solution-polymerized SBR is used as the rubber material for a tire
  • a glass transition temperature of the rubber is increased by increasing a vinyl content in the SBR
  • physical properties, such as running resistance and braking force, required for a tire may not only be controlled, but fuel consumption may also be reduced by appropriately adjusting the glass transition temperature.
  • the solution-polymerized SBR is prepared by using an anionic polymerization initiator, and is being used by coupling or modification of chain ends of the formed polymer using various modifiers.
  • 4,397,994 discloses a technique in which active anions at chain ends of a polymer, which is obtained by polymerization of styrene-butadiene in a non-polar solvent using alkyllithium as a monofunctional initiator, are bonded by using a binder such as a tin compound.
  • Carbon black and silica are being used as a reinforcing filler of a tire's tread, wherein, in a case in which the silica is used as the reinforcing filler, the hysteresis loss may be lowered and the wet road surface resistance may be improved.
  • the silica having a hydrophilic surface has a low affinity with the rubber in comparison to the carbon black having a hydrophobic surface, dispersibility may be poor, and, thus, there is a need to use a separate silane coupling agent to improve the dispersibility or provide coupling between the silica and the rubber. Therefore, a method of introducing a functional group having an affinity or reactivity with the silica into the ends of rubber molecules is being performed, but its effect is insufficient.
  • the present invention provides an amino silane-based compound having an excellent interaction with a rubber polymer and an inorganic filler, a method of preparing the same, a modified conjugated diene-based polymer, in which excellent tensile strength, abrasion resistance, low fuel consumption property, and wet road surface resistance as well as high heat generation property are obtained by including a functional group derived from the amino silane-based compound, and a method of preparing the modified conjugated diene-based polymer.
  • R 1 and R 2 are each independently a hydrocarbon group having 1 to 30 carbon atoms, or a glycol unit represented by
  • R 3 is a divalent hydrocarbon group having 1 to 30 carbon atoms
  • R 4 , R 5 , R 6 , and R 7 are each independently a monovalent hydrocarbon group having 1 to 30 carbon atoms
  • R 8 is a divalent hydrocarbon group having 1 to 10 carbon atoms
  • j and k are each independently 0 or 1
  • n is an integer selected from 1 to 10
  • R 1 and R 2 are glycol units represented by
  • i 1 or 2
  • l is 0 or 1
  • 3-i-l is 1 or 2 when R 1 is a glycol unit represented by
  • i and 1 are each independently 1 or 2, but are not 2 at the same time, and 3-i-l is 0 or 1 when R 2 is a glycol unit represented by and
  • i 1 or 2
  • l is 0 or 1
  • 3-i-l is 0 or 1 when both R 1 and R 2 are glycol units represented by
  • a method of preparing an amino silane-based compound which includes reacting a compound represented by Formula 2 with a compound represented by Formula 3 in a polar solvent:
  • R 3 is a divalent hydrocarbon group having 1 to 30 carbon atoms
  • R 4 , R 5 , R 6 , R 7 , and R 9 are each independently a monovalent hydrocarbon group having 1 to 30 carbon atoms
  • R 8 is a divalent hydrocarbon group having 1 to 10 carbon atoms
  • i is an integer of 1 or 2
  • j, k, and m are each independently an integer of 0 or 1
  • m is 0 or 1 when i is 1
  • m is 0 when i is 2
  • n is an integer selected from 1 to 10
  • X is a leaving group selected from the group consisting of a mesylate group, a tosylate group, and triflate group.
  • a modified conjugated diene-based polymer including the amino silane-based compound-derived function group, and a method of preparing the same.
  • a conjugated diene-based polymer is modified with an amino silane-based compound including a hydrophilic glycol unit having a high affinity with an inorganic filler, particularly, a silica-based filler
  • an amino silane-based compound including a hydrophilic glycol unit having a high affinity with an inorganic filler, particularly, a silica-based filler since a functional group derived from the amino silane-based compound is included at one end of the polymer, preparation of a modified conjugated diene-based polymer having an excellent interaction with the inorganic filler is possible, and the modified conjugated diene-based polymer thus prepared has excellent tensile strength, abrasion resistance, low fuel consumption property, and wet road surface resistance as well as high heat generation property.
  • An amino silane-based compound according to the present invention may be represented by Formula 1 below:
  • R 1 and R 2 may each independently be a hydrocarbon group having 1 to 30 carbon atoms, or a glycol unit represented by
  • R 3 may be a divalent hydrocarbon group having 1 to 30 carbon atoms
  • R 4 , R 5 , R 6 , and R 7 may each independently be a monovalent hydrocarbon group having 1 to carbon atoms
  • R 8 may be a divalent hydrocarbon group having 1 to 10 carbon atoms
  • j and k may each independently be 0 or 1
  • n may be an integer selected from 1 to 10
  • R 1 and R 2 may be a glycol unit represented by
  • i may be 1 or 2
  • l may be 0 or 1
  • 3-i-l may be 1 or 2 when R 1 is a glycol unit represented by
  • i and 1 may each independently be 1 or 2, but may not be 2 at the same time, and 3-i-l may be 0 or 1 when R 2 is a glycol unit represented by and
  • i may be 1 or 2
  • l may be 0 or 1
  • 3-i-l may be 0 or 1 when both R 1 and R 2 are glycol units represented by
  • R 1 and R 2 may each independently be a glycol unit represented by
  • R 3 may be an alkylene group having 1 to 10 carbon atoms
  • R 4 , R 5 , R 6 , and R 7 may each independently be an alkyl group having 1 to 10 carbon atoms
  • R 8 may be an alkylene group having 1 to 5 carbon atoms
  • i may be 1 or 2
  • j, k, and l may each independently be 0 or 1
  • 3-i-l may be 0 or 1
  • n may be an integer selected from 2 to 8.
  • R 1 and R 2 may each independently be a glycol unit represented by
  • R 3 may be an alkylene group having 1 to 5 carbon atoms
  • R 4 , R 5 , R 6 , and R 7 may each independently be an alkyl group having 1 to 5 carbon atoms
  • R 8 may be an alkylene group having 1 to 5 carbon atoms
  • i may be 1 or 2
  • j, k, and l may each independently be 0 or 1
  • 3-i-l may be 0 or 1
  • n may be an integer selected from 3 to 6.
  • amino silane-based compound represented by Formula 1 may be a compound represented by Formula 1-1 below.
  • R 1 may be a glycol unit represented by
  • R 4 , R 5 , R 6 , and R 7 may each independently be a monovalent hydrocarbon group having 1 to 30 carbon atoms
  • R 8 may be a divalent hydrocarbon group having 1 to 10 carbon atoms
  • j and k may each independently be 0 or 1
  • n may be an integer selected from 1 to 10.
  • R 4 , R 5 , R 6 , and R 7 may each independently be a monovalent hydrocarbon group having 1 to 5 carbon atoms
  • R 8 may be a divalent hydrocarbon group having 1 to 5 carbon atoms
  • j and k may each independently be 0 or 1
  • n may be an integer selected from 1 to 5.
  • amino silane-based compound represented by Formula 1 may be a compound represented by Formula 1-2 below.
  • R 1 and R 2 may each independently be a glycol unit represented by
  • R 4 , R 5 , R 6 , and R 7 may each independently be a monovalent hydrocarbon group having 1 to carbon atoms
  • R 8 may be a divalent hydrocarbon group having 1 to 10 carbon atoms
  • j and k may each independently be 0 or 1
  • n may be an integer selected from 1 to 10.
  • R 4 , R 5 , R 6 , and R 7 may each independently be a monovalent hydrocarbon group having 1 to 5 carbon atoms
  • R 8 may be a divalent hydrocarbon group having 1 to 5 carbon atoms
  • j and k may each independently be 0 or 1
  • n may be an integer selected from 1 to 5.
  • amino silane-based compound represented by Formula 1 may be a compound represented by Formula 1-3 below.
  • R 1 may be a glycol unit represented by
  • R 2 , R 4 , R 5 , R 6 , and R 7 may each independently be a monovalent hydrocarbon group having 1 to 30 carbon atoms
  • R 8 may be a divalent hydrocarbon group having 1 to 10 carbon atoms
  • j and k may each independently be 0 or 1
  • n may be an integer selected from 1 to 10.
  • R 2 , R 4 , R 5 , R 6 , and R 7 may each independently be a monovalent hydrocarbon group having 1 to 5 carbon atoms
  • R 8 may be a divalent hydrocarbon group having 1 to 3 carbon atoms
  • j and k may each independently be 0 or 1
  • n may be an integer selected from 1 to 5.
  • the expression “monovalent hydrocarbon group” in the present invention may denote a monovalent atomic group, in which carbon and hydrogen are bonded, such as a monovalent alkyl group, alkenyl group, alkynyl group, cycloalkyl group, cycloalkyl group containing at least one unsaturated bond, and aryl group, and the monovalent atomic group may have a linear or branched structure depending on its bonding structure.
  • divalent hydrocarbon group in the present invention may denote a divalent atomic group, in which carbon and hydrogen are bonded, such as a divalent alkylene group, alkenylene group, alkynylene group, cycloalkylene group, cycloalkylene group containing at least one unsaturated bond, and arylene group, and the divalent atomic group may have a linear or branched structure depending on its bonding structure.
  • the amino silane-based compound represented by Formula 1 may be N,N-bis(3-(triethoxysilyl)propyl)-2,5,8,11,14-pentaoxyhexadecan-16-amine, N,N-bis(3-(diethoxy(methyl)silyl)propyl)-2,5,8,11,14-pentaoxyhexadecan-16-amine, N,N-bis(2-(2-(2-methoxyethoxy)ethoxy)ethyl)3-(triethoxysilyl)propan-1-amine, N,N-bis(2-(2-(2-butoxyethoxy)ethoxy)ethyl)-3-(triethoxysilyl)propan-1-amine, N-(2-(2-methoxyethoxy)ethoxy)-3-(triethoxysilyl)-N-(3-(triethoxysilyl)propyl)propan-1-amine,
  • the amino silane-based compound may be a modifier for modifying a conjugated diene-based polymer.
  • the amino silane-based compound of the present invention may be prepared by a reaction between an amine-based compound containing at least one alkoxysilyl group and a glycol ether-based compound containing a leaving group and a glycol unit.
  • a method of preparing an amino silane-based compound according to the present invention may include a step of reacting a compound represented by the following Formula 2 with a compound represented by the following Formula 3 in a polar solvent:
  • R 3 may be a divalent hydrocarbon group having 1 to 30 carbon atoms
  • R 4 , R 5 , R 6 , R 7 , and R 9 may each independently be a monovalent hydrocarbon group having 1 to 30 carbon atoms
  • R 8 may be a divalent hydrocarbon group having 1 to 10 carbon atoms
  • i may be 1 or 2
  • j, k, and m may each independently be 0 or 1
  • m may be 0 or 1 when i is 1
  • m may be 0 when i is 2
  • n may be an integer selected from 1 to 10
  • X may be a leaving group selected from the group consisting of a mesylate group, a tosylate group, and triflate group.
  • R 3 may be an alkylene group having 1 to 10 carbon atoms
  • R 4 , R 5 , R 6 , and R 7 may each independently be an alkyl group having 1 to 10 carbon atoms
  • R 8 may be an alkylene group having 1 to 5 carbon atoms
  • i may be 1 or 2
  • j, k, and m may each independently be 0 or 1
  • m may be 0 or 1 when i is 1
  • m may be 0 when i is 2
  • n may be an integer selected from 2 to 8, and
  • X may be a mesylate group or a tosylate group.
  • R 3 may be an alkylene group having 1 to 5 carbon atoms
  • R 4 , R 5 , R 6 , and R 7 may each independently be an alkyl group having 1 to 5 carbon atoms
  • R 8 may be an alkylene group having 1 to 5 carbon atoms
  • i may be 1 or 2
  • j, k, and m may each independently be 0 or 1
  • m may be 0 or 1 when i is 1
  • m may be 0 when i is 2
  • n may be an integer selected from 3 to 6
  • X may be a tosylate group.
  • the compound represented by Formula 2 may include 3-(triethoxysilyl)propan-1-amine, bis((ethoxy(methyl)(phenyl)silyl)methyl)amine, bis((diethoxy(methyl)silyl)methyl)amine, 3-(diethoxy (methoxy)silyl)-N-(3-diethoxy(methoxy)silyl)propyl)-2-methylpropan-1-amine, 3-(ethoxydimethoxysilyl)-N-(3-(ethoxydimethoxysilyl)propyl)-2-propan-1-amine, 2-methyl-3-(triethoxysilyl)-N-(3-(triethoxysilyl)propyl)propan-1-amine, 5-(triethoxysilyl)-N-(3-(triethoxysilyl)propyl)pentan-1-amine, N-(3-(trimethoxysilyl)propyl)butan-1
  • the glycol ether-based compound represented by Formula 3 since separation of an atomic group or atomic group ions is easy during a substitution or elimination reaction, the glycol ether-based compound represented by Formula 3 contains a leaving group selected from the group consisting of a mesylate group, a tosylate group, and a triflate group which may be expressed as a good leaving group.
  • a leaving group selected from the group consisting of a mesylate group, a tosylate group, and a triflate group which may be expressed as a good leaving group.
  • the compound represented by Formula 2 and the compound represented by Formula 3 may be used in stoichiometric amounts, and may specifically be used in a molar ratio (Formula 2:Formula 3) of 1:1 to 1:5, 1:1 to 1:3, or 1:1 to 1:2, and the purity and yield of the amino-silane-based compound are excellent within this range.
  • the reaction may be performed at a reaction temperature of 10° C. to 100° C., 20° C. to 90° C., or 50° C. to 80° C., and the purity and yield of the amino-silane-based compound are excellent within this range.
  • the reaction may be performed by including a polar additive, and, as a specific example, the polar additive may be an inorganic material or an organic material, wherein the inorganic polar additive, for example, may include a hydride containing an alkali metal or alkaline earth metal; a hydroxide containing an alkali metal or alkaline earth metal; or a carbonate containing an alkali metal or alkaline earth metal, any one thereof or a mixture of two or more thereof may be used, the organic polar additive, for example, may include an amine-based base; or an alkoxy-based base, and any one thereof or a mixture of two or more thereof may be used.
  • the polar additive may be triethylamine.
  • the polar additive may act as a Lewis base for removing protons remaining in an amine group (Lewis acid) after the reaction, and, in a case in which the reaction is performed by including the polar additive, a reaction rate is improved, and the purity and yield of the amino-silane-based compound are excellent.
  • the polar solvent may be a polar aprotic solvent
  • specific examples of the polar solvent may be an amide-based solvent; an ether-based solvent; a ketone-based solvent; a sulfoxide-based solvent; a nitrile-based solvent; or an alcohol-based solvent such as isopropyl alcohol (IPA), and any one thereof or a mixture of two or more thereof may be used.
  • the polar solvent may be acetonitrile.
  • a modified conjugated diene-based polymer according to the present invention may include a conjugated diene-based monomer-derived repeating unit, and may include an amino silane-based compound-derived function group represented by the following Formula 1 at one end.
  • the conjugated diene-based monomer-derived repeating unit may denote a repeating unit formed by polymerization of a conjugated diene-based monomer
  • the conjugated diene-based monomer for example, may include at least one selected from the group consisting of 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, piperylene, 3-butyl-1,3-octadiene, isoprene, 2-phenyl-1,3-butadiene, and 2-halo-1,3-butadiene (the expression “halo” denotes a halogen atom).
  • the modified conjugated diene-based polymer may be a copolymer further including an aromatic vinyl monomer-derived repeating unit in addition to the conjugated diene-based monomer-derived repeating unit.
  • the aromatic vinyl monomer-derived repeating unit may denote a repeating unit formed by polymerization of an aromatic vinyl monomer, and the aromatic vinyl monomer, for example, may include at least one selected from the group consisting of styrene, ⁇ -methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-propylstyrene, 1-vinylnaphthalene, 4-cyclohexylstyrene, 4-(p-methylphenyl)styrene, and 1-vinyl-5-hexylnaphthalene.
  • the modified conjugated diene-based polymer may include the conjugated diene-based monomer-derived repeating unit in an amount of 50 wt % to 95 wt %, 55 wt % to 90 wt %, or 60 wt % to 90 wt %, and the aromatic vinyl monomer-derived repeating unit in an amount of 5 wt % to 50 wt %, 10 wt % to 45 wt %, or 10 wt % to 40 wt %, and rolling resistance, wet road surface resistance, and abrasion resistance are excellent within this range.
  • the copolymer may be a random copolymer, and, in this case, a balance between physical properties is excellent.
  • the random copolymer may denote that repeating units constituting the copolymer are disorderly arranged.
  • the modified conjugated diene-based polymer according to an embodiment of the present invention may have a number-average molecular weight (Mn) of 10,000 g/mol to 2,000,000 g/mol, 100,000 g/mol to 1,500,000 g/mol, or 200,000 g/mol to 800,000 g/mol, and may have a weight-average molecular weight (Mw) of 10,000 g/mol to 5,000,000 g/mol, 150,000 g/mol to 3,000,000 g/mol, or 300,000 g/mol to 1,500,000 g/mol, and the rolling resistance and wet road surface resistance are excellent within this range.
  • the modified conjugated diene-based polymer may have a molecular weight distribution (Mw/Mn) of 1.0 to 5.0, 1.1 to 3.0, or 1.3 to 3.0, and the balance between physical properties is excellent within this range.
  • the modified conjugated diene-based polymer may have a Mooney viscosity (MV) at 100° C. of 20 to 180, 40 to 150, 60 to 110, or 80 to 110, and processability and productivity are excellent within this range.
  • MV Mooney viscosity
  • the modified conjugated diene-based polymer may have a vinyl content of 5 wt % or more, 10 wt % or more, or 10 wt % to 50 wt %, and, since a glass transition temperature may be adjusted to an appropriate range, the rolling resistance, wet road surface resistance, and low fuel consumption property are excellent within this range.
  • the vinyl content may denote a content of a 1,2-added conjugated diene-based monomer rather than a 1,4-added conjugated diene-based monomer based on 100 wt % of the conjugated diene-based copolymer composed of a monomer having a vinyl group and an aromatic vinyl-based monomer.
  • derived repeating unit and “derived functional group” in the present invention may denote a component or structure generated from a certain material or may denote the material itself.
  • a method of preparing a modified conjugated diene-based polymer according to the present invention may include a step (S1) of preparing an active polymer coupled with an organometal by polymerization of a conjugated diene-based monomer, or an aromatic vinyl-based monomer with a conjugated diene-based monomer in a hydrocarbon solvent including an organometallic compound; and a step (S2) of reacting the active polymer with an amino silane-based compound represented by Formula 1 below.
  • the hydrocarbon solvent is not particularly limited, but, for example, may be at least one selected from the group consisting of n-pentane, n-hexane, n-heptane, isooctane, cyclohexane, toluene, benzene and xylene.
  • the compound represented by Formula 1 may be used in an amount of 0.01 mmol to 10 mmol, 0.05 mmol to 5 mmol, 0.1 mmol to 2 mmol, or 0.1 mmol to 1 mmol based on total 100 g of the monomer.
  • the organometallic compound may be used in an amount of 0.01 mmol to 10 mmol, 0.05 mmol to 5 mmol, 0.1 mmol to 2 mmol, or 0.1 mmol to 1 mmol based on total 100 g of the monomer.
  • the organometallic compound may include at least one selected from the group consisting of methyllithium, ethyllithium, propyllithium, n-butyllithium, s-butyllithium, t-butyllithium, hexyllithium, n-decyllithium, t-octyllithium, phenyllithium, 1-naphthyllithium, n-eicosyllithium, 4-butylphenyllithium, 4-tolyllithium, cyclohexyllithium, 3,5-di-n-heptylcyclohexyllithium, 4-cyclopentyllithium, naphtylsodium, naphtylpotassium, lithium alkoxide, sodium alkoxide, potassium alkoxide, lithium sulfonate, sodium sulfonate, potassium sulfonate, lithium amide, sodium amide, potassium amide, and lithium
  • the polymerization of the step (S1) may be performed by including a polar additive, and the polar additive may be added in an amount of 0.001 g to 50 g, 0.001 g to 10 g, or 0.005 g to 0.1 g based on total 100 g of the monomer.
  • the polar additive may be at least one selected from the group consisting of tetrahydrofuran, ditetrahydrofurylpropane, diethylether, cycloamylether, dipropyl ether, ethylene dimethyl ether, diethyl glycol, dimethyl ether, tertiary butoxyethoxyethane, bis(3-dimethylaminoethyl)ether, (dimethylaminoethyl)ethylether, trimethylamine, triethylamine, tripropylamine, and tetramethylethylenediamine, and, for example, may be triethylamine or tetramethylethylenediamine, the polar additive may be the same or different from a polar additive which may be added during the preparation of the amino silane-based compound, and, in a case in which the conjugated diene-based monomers, or the conjugated diene-based monomer and the aromatic vinyl-based monomer are copolymerized
  • the polymerization of the step (S1) may be anionic polymerization, and, specifically, may be living anionic polymerization in which an anionic active site at polymerization end is obtained by a growth polymerization reaction by anions.
  • the polymerization of the step (S1) may be temperature rise polymerization, isothermal polymerization, or constant temperature polymerization (adiabatic polymerization)
  • the constant temperature polymerization may denote a polymerization method including a step of performing polymerization not by randomly applying heat but with its own reaction heat after an organometallic compound is added
  • the temperature rise polymerization may denote a polymerization method in which the temperature is increased by randomly applying heat after the organometallic compound is added
  • the isothermal polymerization may denote a polymerization method in which the temperature of the polymer is constantly maintained by taking away heat or applying heat after the organometallic compound is added.
  • the polymerization of the step (S1) for example, may be performed in a temperature range of ⁇ 20°
  • the active polymer prepared in the step (S1) may denote a polymer in which a polymeric anion is combined with an organometallic cation.
  • the amino silane-based compound represented by Formula 1 may be used in an amount of 0.01 mol to 10 mol, 0.05 mol to 5 mol, or 0.1 mol to 2 mol with respect to 1 mol of the organometallic compound, and, since the optimal modification reaction may be performed within this range, a conjugated diene-based polymer having a high modification ratio may be obtained.
  • the reaction of the step (S2) is a modification reaction for the introduction of a functional group derived from the amino silane-based compound into the active polymer, wherein the reaction may be performed in a temperature range of 0° C. to 90° C. for 1 minute to 5 hours.
  • the method of preparing a modified conjugated diene-based polymer may be performed by a batch polymerization method or a continuous polymerization method including one or more reactors.
  • the method of preparing a modified conjugated diene-based polymer may further include at least one step of recovering solvent and unreacted monomer and drying, if necessary, after the step (S2).
  • a rubber composition including the above-described modified conjugated diene-based polymer.
  • the rubber composition may include the modified conjugated diene-based polymer in an amount of 10 wt % or more, 10 wt % to 100 wt %, or 20 wt % to 90 wt %, and mechanical properties, such as tensile strength and abrasion resistance, are excellent and the balance between physical properties is excellent within this range.
  • the rubber composition may further include another rubber component, if necessary, in addition to the modified conjugated diene-based polymer, and, in this case, the rubber component may be included in an amount of 90 wt % or less based on a total weight of the rubber composition. Specifically, the other rubber component may be included in an amount of 1 part by weight to 900 parts by weight based on 100 parts by weight of the modified conjugated diene-based polymer.
  • the rubber component may be a natural rubber or a synthetic rubber, and specific examples of the rubber component may be a natural rubber (NR) including cis-1,4-polyisoprene; a modified natural rubber, such as an epoxidized natural rubber (ENR), a deproteinized natural rubber (DPNR), and a hydrogenated natural rubber, in which the general natural rubber is modified or purified; and a synthetic rubber such as a styrene-butadiene rubber (SBR), polybutadiene (BR), polyisoprene (IR), a butyl rubber (IIR), an ethylene-propylene copolymer, polyisobutylene-co-isoprene, neoprene, poly(ethylene-co-propylene), poly(styrene-co-butadiene), poly(styrene-co-isoprene), poly(styrene-co-isoprene-co-butadiene), poly(sty
  • the rubber composition may include 0.1 part by weight to 200 parts by weight or 10 parts by weight to 120 parts by weight of a filler based on 100 parts by weight of the modified conjugated diene-based polymer of the present invention.
  • the filler for example, may be a silica-based filler, specific examples of the silica-based filler may be wet silica (hydrous silicic acid), dry silica (anhydrous silicic acid), calcium silicate, aluminum silicate, or colloidal silica, and the filler may preferably be wet silica in which an effect of improving both fracture characteristics and wet grip is the most significant.
  • the rubber composition may further include a carbon black-based filler, if necessary.
  • silane coupling agent for the improvement of reinforcement and low heat generation property may be used together.
  • the silane coupling agent may be bis(3-triethoxysilylpropyl)tetrasulfide, bis(3-triethoxysilylpropyl)trisulfide, bis(3-triethoxysilylpropyl)disulfide, bis(2-triethoxysilylethyl)tetrasulfide, bis(3-trimethoxysilylpropyl)tetrasulfide, bis(2-trimethoxysilylethyl)tetrasulfide, 3-mercaptopropyl trimethoxysilane, 3-mercaptopropyl triethoxysilane, 2-mercaptoethyl trimethoxysilane, 2-mercaptoethyl triethoxysilane, 3-trimethoxysilyl
  • the silane coupling agent may preferably be bis(3-triethoxysilylpropyl)polysulfide or 3-trimethoxysilylpropyl benzothiazyl tetrasulfide.
  • the modified conjugated diene-based polymer in which a function group having a high affinity with the silica is introduced into the active site, is used as the rubber component, a mixing amount of the silane coupling agent may be reduced in comparison to a conventional case.
  • the silane coupling agent may be used in an amount of 1 part by weight to 20 parts by weight or 5 parts by weight to 15 parts by weight based on 100 parts by weight of the silica. Within this range, the silane coupling agent may prevent gelation of the rubber component while sufficiently having an effect as a coupling agent.
  • the rubber composition according to the embodiment of the present invention may be sulfur cross-linkable, and may further include a vulcanizing agent.
  • the vulcanizing agent may specifically be sulfur powder, and may be included in an amount of 0.1 part by weight to 10 parts by weight based on 100 parts by weight of the rubber component, and, within this range, the low fuel consumption property is excellent while securing elastic modulus and strength required for the vulcanized rubber composition.
  • the rubber composition according to the embodiment of the present invention may further include various additives, such as a vulcanization accelerator, process oil, a plasticizer, an antioxidant, a scorch inhibitor, zinc white, stearic acid, a thermosetting resin, or a thermoplastic resin, used in the general rubber industry, in addition to the above-described components.
  • additives such as a vulcanization accelerator, process oil, a plasticizer, an antioxidant, a scorch inhibitor, zinc white, stearic acid, a thermosetting resin, or a thermoplastic resin, used in the general rubber industry, in addition to the above-described components.
  • a thiazole-based compound such as 2-mercaptobenzothiazole (M), dibenzothiazyl disulfide (DM), and N-cyclohexylbenzothiazole-2-sulfenamide (CZ), or a guanidine-based compound, such as diphenylguanidine (DPG), may be used as the vulcanization accelerator, and the vulcanization accelerator may be included in an amount of 0.1 part by weight to 5 parts by weight based on 100 parts by weight of the rubber component.
  • M 2-mercaptobenzothiazole
  • DM dibenzothiazyl disulfide
  • CZ N-cyclohexylbenzothiazole-2-sulfenamide
  • DPG diphenylguanidine
  • the process oil acts as a softener in the rubber composition, wherein examples of the process oil may be a paraffin-based, naphthenic-based, or aromatic-based compound, the aromatic-based process oil may be used in consideration of tensile strength and abrasion resistance, and the naphthenic-based or paraffin-based process oil may be used in consideration of hysteresis loss and low temperature characteristics.
  • the process oil may be included in an amount of 100 parts by weight or less based on 100 parts by weight of the rubber component, and, within this range, decreases in tensile strength and low heat generation property (low fuel consumption property) of the vulcanized rubber may be prevented.
  • antioxidant may be N-isopropyl-N′-phenyl-p-phenylenediamine, N-(1,3-dimethylbutyl)-N′-phenyl-p-phenylenediamine, 6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline, or a high-temperature condensate of diphenylamine and acetone, and the antioxidant may be used in an amount of 0.1 part by weight to 6 parts by weight based on 100 parts by weight of the rubber component.
  • the rubber composition according to the embodiment of the present invention may be obtained by kneading the above mixing formulation using a kneader such as a Banbury mixer, a roll, and an internal mixer, and a rubber composition having excellent abrasion resistance as well as low heat generation property may also be obtained by a vulcanization process after molding.
  • a kneader such as a Banbury mixer, a roll, and an internal mixer
  • the rubber composition may be suitable for the preparation of each member of a tire, such as a tire's tread, an under tread, a sidewall, a carcass coating rubber, a belt coating rubber, a bead filler, a chafer, or a bead coating rubber, or various industrial rubber products such as an anti-vibration rubber, a belt conveyor, and a hose.
  • a tire's tread such as a tire's tread, an under tread, a sidewall, a carcass coating rubber, a belt coating rubber, a bead filler, a chafer, or a bead coating rubber
  • various industrial rubber products such as an anti-vibration rubber, a belt conveyor, and a hose.
  • the present invention provides a tire prepared by using the rubber composition.
  • the tire may include a tire or a tire's tread.
  • n-hexane 85 wt % of n-hexane, from which impurities, such as moisture, were removed, and 15 wt % of a monomer mixture (73 wt % of butadiene and 27 wt % of styrene) were continuously added at a total flow rate of 400 g/hr to a raw material input line of a first reactor among three continuous stirred-tank reactors (CSTR).
  • CSTR continuous stirred-tank reactors
  • n-butyllithium for initiating a reaction was added to the input line, and ditetrahydrofurylpropane (DTP), as a polar additive, was added in a molar ratio of 0.5 to 3 with respect to a molar amount of the n-butyllithium.
  • DTP ditetrahydrofurylpropane
  • an internal temperature of the reactor was controlled to be in a range of 70° C. to 85° C. and was maintained for 30 minutes to 60 minutes.
  • a polymer of the first reactor thus obtained was continuously supplied to the top of a second reactor, and an internal temperature of the reactor was controlled to be in a range of 70° C. to 85° C. and was maintained for 60 minutes so that a polymerization conversion rate was 90%.
  • a polymer of the second reactor thus obtained was continuously supplied to the top of a third reactor, the compound represented by Formula 1a, which was prepared in Preparation Example 1, was continuously supplied in a molar amount equivalent to that of the n-butyllithium to perform a modification reaction.
  • a solution including 5 wt % to 10 wt % of ethyl alcohol and 25 wt % to 35 wt % of an antioxidant (Wingstay-K) was added to a polymer of the third reactor thus obtained at a rate of 1.005 ml/min to stop the polymerization reaction, and a polymer was obtained.
  • the polymer obtained was put in hot water heated by steam and stirred to remove the solvent, the residual solvent and water were removed by roll drying to prepare a modified conjugated diene-based polymer.
  • Table 1 The results of the analysis of the modified conjugated diene-based polymer thus prepared are presented in Table 1 below.
  • Example 2 was performed in the same manner as in Example 1 except that the compound represented by Formula 1b which was prepared in Preparation Example 2, instead of the compound represented by Formula 1a which was prepared in Preparation Example 1, was added in the same molar amount in Example 1.
  • Example 3 was performed in the same manner as in Example 1 except that the compound represented by Formula 1d which was prepared in Preparation Example 4, instead of the compound represented by Formula 1a which was prepared in Preparation Example 1, was added in the same molar amount in Example 1.
  • Example 4 was performed in the same manner as in Example 1 except that the compound represented by Formula 1e which was prepared in Preparation Example 5, instead of the compound represented by Formula 1a which was prepared in Preparation Example 1, was added in the same molar amount in Example 1.
  • Example 5 was performed in the same manner as in Example 1 except that the compound represented by Formula 1g which was prepared in Preparation Example 7, instead of the compound represented by Formula 1a which was prepared in Preparation Example 1, was added in the same molar amount in Example 1.
  • Example 6 was performed in the same manner as in Example 1 except that the compound represented by Formula 1h which was prepared in Preparation Example 8, instead of the compound represented by Formula 1a which was prepared in Preparation Example 1, was added in the same molar amount in Example 1.
  • Comparative Example 1 was performed in the same manner as in Example 1 except that the compound represented by Formula 1a, which was prepared in Preparation Example 1, was not added in Example 1.
  • a weight-average molecular weight (Mw, ⁇ 10 3 g/mol), a number-average molecular weight (Mn, ⁇ 10 3 g/mol), a molecular weight distribution (MWD), and Mooney viscosity (MV) were respectively measured for the modified or unmodified conjugated diene-based polymers prepared in the examples and comparative example. The results thereof are presented in Table 1 below.
  • the weight-average molecular weight (Mw) and the number-average molecular weight (Mn) were measured by gel permeation chromatograph (GPC) analysis, and the molecular weight distribution (MWD, Mw/Mn) was obtained by calculation using each molecular weight measured.
  • GPC gel permeation chromatograph
  • Mw/Mn molecular weight distribution
  • the Mooney viscosity (MV, (ML1+4, @100° C.) MU) was measured with a large rotor at a rotor speed of 2 ⁇ 0.02 rpm at 100° C. using MV-2000 (ALPHA Technologies). After samples used in this case were left standing for 30 minutes or more at room temperature (23 ⁇ 3° C.), 27 ⁇ 3 g of each sample was taken and filled into a die cavity, and the Mooney viscosity was measured for 4 minutes by operating a platen.
  • Each of the modified or unmodified styrene-butadiene copolymers of the examples and comparative example was used as a raw material rubber and was mixed under mixing conditions shown in Table 2 below. An amount of each raw material in Table 2 was represented by parts by weight based on 100 parts by weight of the rubber.
  • the rubber samples were kneaded through first stage kneading and second stage kneading.
  • the raw material rubber styrene-butadiene copolymer
  • filler styrene-butadiene copolymer
  • organosilane coupling agent styrene-butadiene copolymer
  • process oil zinc white
  • stearic acid stearic acid
  • antioxidant anti-aging agent
  • wax wax
  • an initial temperature of the mixer was controlled to be 70° C. and, after the completion of the mixing, a formulation obtained at a discharge temperature of 150° C. to 160° C. was formed into a synthetic rubber sheet with a roll mill set at 50° C.
  • the primary formulation was cooled to room temperature
  • the primary formulation, sulfur, a primary vulcanization accelerator and a secondary vulcanization accelerator were added to the mixer, mixing was performed in a state in which the temperature of the mixer was controlled to be 40° C., and a formulation obtained at a discharge temperature of 110° C. or less was formed into a synthetic rubber sheet with a roll mill set at 50° C. to obtain a secondary formulation.
  • a curing process was performed at 160° C. for 20 minutes to 30 minutes to prepare each rubber sample.
  • Each specimen was prepared according to the tensile test method of ASTM 412, and tensile strength at break of the specimen and tensile stress at 300% elongation (300% modulus) were measured for tensile properties. Specifically, the tensile properties were measured at a rate of 50 cm/min at room temperature using a tensile testing machine, a Universal Test Machine 4204 (Instron).
  • Abrasion resistances of the rubber samples prepared were measured using a DIN abrasion tester in such a manner that, after a load of 10 N was applied to a rotating drum with abrasive paper and each rubber sample was moved in a direction perpendicular to a rotational direction of the drum, an abrasion weight loss was measured.
  • a rotational speed of the drum was 40 rpm, and a total movement of the sample at the completion of the test was 40 m. The smaller the weight loss was, the better the abrasion resistance was.
  • tan ⁇ was measured in a torsion mode at a frequency of 10 Hz while changing a strain at each measurement temperature ( ⁇ 60° C. to 70° C.) using a dynamic mechanical analyzer (TA Instruments).
  • the Payne effect was expressed as the difference between the maximum value and the minimum value at a strain of 0.28% to 40%.
  • the higher the tan ⁇ at a low temperature of 0° C. was, the better the wet road surface resistance was, and the lower the tan ⁇ at a high temperature of 60° C. was, the lower the hysteresis loss was and the better the low running resistance (fuel economy) was.

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EP3524638A1 (de) 2019-08-14
EP3524638A4 (de) 2019-08-14
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